Glass, glass-ceramic and ceramic articles with durable lubricious anti-fingerprint coatings over optical and scratch-resistant coatings and methods of making the same

ABSTRACT

An article is described herein that includes: a glass, glass-ceramic or ceramic substrate comprising a primary surface; at least one of an optical film and a scratch-resistant film disposed over the primary surface; and an easy-to-clean (ETC) coating comprising a fluorinated material that is disposed over an outer surface of the at least one of an optical film and a scratch-resistant film. The at least one of an optical film and a scratch-resistant film comprises an average hardness of 10 GPa or more. Further, the outer surface of the at least one of an optical film and a scratch-resistant film comprises a surface roughness (Rq) of less than 1.0 nm.

CLAIM OF PRIORITY

This application is a continuation application of U.S. patentapplication Ser. No. 15/974,188, filed May 8, 2018, now pending, whichclaims the benefit of priority under 35 U.S.C. § 119 of U.S. ProvisionalApplication Ser. No. 62/502,911 filed on May 8, 2017; the entirecontents of each of these documents are hereby incorporated herein byreference for all purposes.

FIELD

The present disclosure generally relates to glass, glass-ceramic andceramic articles with durable lubricious coatings over optical coatingsand/or scratch-resistant coatings, along with methods of making thesame.

BACKGROUND

Glass, glass-ceramic and ceramic materials, many of which are configuredor otherwise processed with various strength-enhancing features, areprevalent in various displays and display devices of many consumerelectronic products. For example, chemically strengthened glass isfavored for many touch-screen products, including cell phones, musicplayers, e-book readers, notepads, tablets, laptop computers, automaticteller machines, and other similar devices. Many of these glass,glass-ceramic and ceramic materials are also employed in displays anddisplay devices of consumer electronic products that do not havetouch-screen capability, but are prone to direct human contact,including desktop computers, laptop computers, elevator screens,equipment displays, and others.

These glass, glass-ceramic and ceramic materials, however, are oftensubject to human contact that can result in surface contamination,visible fingerprints, staining, and other foreign substances that canaffect optical clarity of the displays and display devices employingthese materials. In addition, these displays and display devicesfrequently employ optical coatings, such as anti-reflective (AR)coatings that are particularly prone to surface contamination, stainsand the like from direct human contact. Further, these unwanted foreignsubstances can negatively affect the aesthetics of the productsemploying these displays and display devices. In addition, thesereductions in optical clarity can cause a user to increase thebrightness of the display device, leading to increased battery usage andless time between charging evolutions.

In view of these considerations and drawbacks associated with glass,glass-ceramic and ceramic material surfaces, many consumer electronicproducts employing these materials also feature an easy-to-clean (ETC)coating over any surfaces of the glass, glass-ceramic and ceramicsubstrates exposed to human contact and any other optical coatings, ifpresent. Many of these ETC coatings contain one or more fluorinatedmaterials. These ETC coatings are generally hydrophobic and oleophobicin nature, and can also be referred to as “anti-fingerprint,”“lubricious” or “anti-smudge” coatings. Among the benefits offered byETC coatings is an added degree of ease in removing fingerprints, stainsand other surface contamination from these glass, glass-ceramic andceramic materials. ETC coatings, given their hydrophobic and oleophobicnature, are also less likely to retain or be prone to surfacecontamination from human contact in the first instance.

While ETC coatings offer many benefits to electronic products employingglass, glass-ceramic and ceramic materials in their displays and displaydevices, the coatings themselves can be sensitive to wear. For example,wear associated with these coatings can negatively affect theirhydrophobicity and/or oleophobicity, which can reduce the ability of thecoating to perform as intended. In addition, the wear associated withthese ETC coatings can be exacerbated by the presence of an opticalcoating and/or scratch-resistant coating between the ETC coating and theglass, glass-ceramic or ceramic materials, as these intervening coatingscan have increased roughness relative to the outer surface of the glass,glass-ceramic or ceramic material itself.

Efforts to improve the durability of these ETC coatings have involvedadjusting the composition of the coatings and processing conditions(e.g., curing conditions) with limited degrees of success. Efforts toincrease the thickness of these ETC coatings to enhance long-termdurability also have had little success, as such efforts often come atthe expense of reduced optical properties of the articles employing theETC coatings, increased manufacturing cost and increased process controlvariability of the coating deposition.

In view of these considerations, there is a need for glass,glass-ceramic and ceramic articles, particularly those employingscratch-resistant and optical films, with lubricious ETC coatings havinghigh durability, along with methods of making the same.

SUMMARY

An aspect of this disclosure pertains to an article that includes: aglass, glass-ceramic or ceramic substrate comprising a primary surface;at least one of an optical film and a scratch-resistant film disposedover the primary surface; and an easy-to-clean (ETC) coating comprisinga fluorinated material that is disposed over an outer surface of the atleast one of an optical film and a scratch-resistant film. The at leastone of an optical film and a scratch-resistant film comprises an averagehardness of 12 GPa or more. Further, the outer surface of the at leastone of an optical film and a scratch-resistant film comprises a surfaceroughness (R_(q)) of less than 1.0 nm. In other aspects of thedisclosure, the at least one of an optical film and a scratch-resistantfilm can comprise a total thickness of about 500 nm or more. Accordingto some implementations, the at least one of an optical film and ascratch-resistant film can comprise a total thickness of about 1500 nmor more.

A further aspect of this disclosure pertains to an article thatincludes: a glass, glass-ceramic or ceramic substrate comprising aprimary surface; at least one of an optical film and a scratch-resistantfilm disposed over the primary surface; and an easy-to-clean (ETC)coating comprising a fluorinated material that is disposed over an outersurface of the at least one of an optical film and a scratch-resistantfilm. The at least one of an optical film and a scratch-resistant filmcomprises a total thickness of about 500 nm or more. Further, the outersurface of the at least one of an optical film and a scratch-resistantfilm comprises a surface roughness (R_(q)) of less than 1.0 nm.According to some implementations, the at least one of an optical filmand a scratch-resistant film can comprise a total thickness of about1500 nm or more.

In embodiments of these aspects, the outer surface of the at least oneof an optical film and a scratch-resistant film comprises a surfaceroughness (R_(q)) of less than 0.7 nm. In other embodiments, the outersurface of the at least one of an optical film and a scratch-resistantfilm comprises a surface roughness (R_(q)) of less than 0.5 nm.

According to some implementations of these aspects, the exposed surfaceof the ETC coating comprises an average contact angle with water of 100degrees or more after being subjected to 2000 reciprocating cycles undera load of 1 kg, according to a Steel Wool Test. In otherimplementations, the exposed surface of the ETC coating comprises anaverage contact angle with water of 100 degrees or more after beingsubjected to 3500 reciprocating cycles under a load of 1 kg, accordingto the Steel Wool Test. In aspects of the disclosure, including theseimplementations, the ETC coating of the article comprises aperfluoropolyether (PFPE) silane.

In further implementations of these aspects, the at least one of anoptical film and a scratch-resistant film can comprise ascratch-resistant film comprising an AlO_(x)N_(y) material. In otheraspects of the disclosure the at least one of an optical film and ascratch-resistant film comprises a scratch-resistant film that comprisesa Si_(u)Al_(x)O_(y)N_(z) material. In some implementations of thesearticles, the article further comprises an optical film and thescratch-resistant film is disposed over the optical film. In someembodiments of these articles the substrate comprises a glasscomposition and a compressive stress region, the compressive stressregion extending from the primary surface to a first selected depth inthe substrate.

In an additional implementation of these aspects, a consumer electronicdevice is provided that includes: a housing a having a front surfaced, aback surface and side surfaces; electrical components provided at leastpartially within the housing, the electrical components including atleast a controller, a memory, and a display, the display being providedat or adjacent to the front surface of the housing; and a cover glassdisposed over the display. Further, at least one of a portion of thehousing or the cover glass comprises the article of any one of theforegoing articles.

Additional features and advantages will be set forth in the detaileddescription which follows, and will be readily apparent to those skilledin the art from that description or recognized by practicing theembodiments as described herein, including the detailed descriptionwhich follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary, and areintended to provide an overview or framework to understanding the natureand character of the disclosure and the appended claims.

The accompanying drawings are included to provide a furtherunderstanding of principles of the disclosure, and are incorporated in,and constitute a part of, this specification. The drawings illustrateone or more embodiment(s) and, together with the description, serve toexplain, by way of example, principles and operation of the disclosure.It is to be understood that various features of the disclosure disclosedin this specification and in the drawings can be used in any and allcombinations. By way of non-limiting examples, the various features ofthe disclosure may be combined with one another according to thefollowing embodiments.

According to a first aspect, an article is provided that includes: aglass, glass-ceramic or ceramic substrate comprising a primary surface;at least one of an optical film and a scratch-resistant film disposedover the primary surface; and an easy-to-clean (ETC) coating comprisinga fluorinated material that is disposed over an outer surface of the atleast one of an optical film and a scratch-resistant film. The at leastone of an optical film and a scratch-resistant film comprises an averagehardness of 12 GPa or more. Further, the outer surface of the at leastone of an optical film and a scratch-resistant film comprises a surfaceroughness (R_(q)) of less than 1.0 nm.

According to a second aspect, the article of aspect 1 is provided,wherein the outer surface of the at least one of an optical film and ascratch-resistant film comprises a surface roughness (R_(q)) of lessthan 0.7 nm.

According to a third aspect, the article of aspect 1 is provided,wherein the outer surface of the at least one of an optical film and ascratch-resistant film comprises a surface roughness (R_(q)) of lessthan 0.5 nm.

According to a fourth aspect, any one of aspects 1-3 is provided,wherein an exposed surface of the ETC coating comprises an averagecontact angle with water of 100 degrees or more after being subjected to2000 reciprocating cycles under a load of 1 kg according to a Steel WoolTest.

According to a fifth aspect, any one of aspects 1-3 is provided, whereinan exposed surface of the ETC coating comprises an average contact anglewith water of 100 degrees or more after being subjected to 3500reciprocating cycles under a load of 1 kg according to a Steel WoolTest.

According to a sixth aspect, any one of aspects 1-5 is provided, whereinthe ETC coating comprises a perfluoropolyether (PFPE) silane.

According to a seventh aspect, any one of aspects 1-6 is provided,wherein the at least one of an optical film and a scratch-resistant filmcan comprise a scratch-resistant film comprising an AlO_(x)N_(y)material

According to an eighth aspect, any one of aspects 1-7 is provided,wherein the at least one of an optical film and a scratch-resistant filmcomprises a scratch-resistant film that comprises aSi_(u)Al_(x)O_(y)N_(z) material.

According to a ninth aspect, any one of aspects 1-8 is provided, whereinthe at least one of an optical film and a scratch-resistant film furthercomprises an optical film and the scratch-resistant film is disposedover the optical film.

According to a tenth aspect, any one of aspects 1-9 is provided, whereinthe substrate comprises a glass composition and a compressive stressregion, the compressive stress region extending from the primary surfaceto a first selected depth in the substrate.

According to an eleventh aspect, any one of aspects 1-10 is provided,wherein the at least one of an optical film and a scratch-resistant filmcomprises a total thickness of about 500 nm or more.

According to a twelfth aspect, any one of aspects 1-11 is provided,wherein the at least one of an optical film and a scratch-resistant filmcomprises a total thickness of about 500 nm or more.

According to a thirteenth aspect, an article is provided that includes:a glass, glass-ceramic or ceramic substrate comprising a primarysurface; at least one of an optical film and a scratch-resistant filmdisposed over the primary surface; and an easy-to-clean (ETC) coatingcomprising a fluorinated material that is disposed over an outer surfaceof the at least one of an optical film and a scratch-resistant film. Theat least one of an optical film and a scratch-resistant film comprises atotal thickness of about 500 nm or more. Further, the outer surface ofthe at least one of an optical film and a scratch-resistant filmcomprises a surface roughness (R_(q)) of less than 1.0 nm.

According to a fourteenth aspect, the article of aspect 13 is provided,wherein the outer surface of the at least one of an optical film and ascratch-resistant film comprises a surface roughness (R_(q)) of lessthan 0.7 nm.

According to a fifteenth aspect, the article of aspect 13 is provided,wherein the outer surface of the at least one of an optical film and ascratch-resistant film comprises a surface roughness (R_(q)) of lessthan 0.5 nm.

According to a sixteenth aspect, any one of aspects 13-15 is provided,wherein an exposed surface of the ETC coating comprises an averagecontact angle with water of 100 degrees or more after being subjected to2000 reciprocating cycles under a load of 1 kg according to a Steel WoolTest.

According to a seventeenth aspect, any one of aspects 13-15 is provided,wherein an exposed surface of the ETC coating comprises an averagecontact angle with water of 100 degrees or more after being subjected to3500 reciprocating cycles under a load of 1 kg according to a Steel WoolTest.

According to an eighteenth aspect, any one of aspects 13-17 is provided,wherein the ETC coating comprises a perfluoropolyether (PFPE) silane.

According to a nineteenth aspect, any one of aspects 13-18 is provided,wherein the at least one of an optical film and a scratch-resistant filmcan comprise a scratch-resistant film comprising an AlO_(x)N_(y)material

According to a twentieth aspect, any one of aspects 13-19 is provided,wherein the at least one of an optical film and a scratch-resistant filmcomprises a scratch-resistant film that comprises aSi_(u)Al_(x)O_(y)N_(z) material.

According to a twenty-first aspect, any one of aspects 13-20 isprovided, wherein the at least one of an optical film and ascratch-resistant film further comprises an optical film and thescratch-resistant film is disposed over the optical film.

According to a twenty-second aspect, any one of aspects 13-21 isprovided, wherein the substrate comprises a glass composition and acompressive stress region, the compressive stress region extending fromthe primary surface to a first selected depth in the substrate.

According to a twenty-third aspect, any one of aspects 13-22 isprovided, wherein the at least one of an optical film and ascratch-resistant film comprises a total thickness of about 1500 nm ormore.

According to a twenty-fourth aspect, a consumer electronic product isprovided that includes: a housing a having a front surfaced, a backsurface and side surfaces; electrical components provided at leastpartially within the housing, the electrical components including atleast a controller, a memory, and a display, the display being providedat or adjacent to the front surface of the housing; and a cover glassdisposed over the display. Further, at least one of a portion of thehousing or the cover glass comprises the article of any one of aspects1-23.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects and advantages of the presentdisclosure are better understood when the following detailed descriptionof the disclosure is read with reference to the accompanying drawings,in which:

FIG. 1A is a cross-sectional, schematic view of a glass articlecomprising a glass substrate with an optical film, scratch-resistantfilm and an ETC coating disposed over the substrate, according to someaspects of the disclosure.

FIG. 1B is a cross-sectional, schematic view of a glass articlecomprising a glass substrate with a scratch-resistant film and an ETCcoating disposed over the substrate, according to some aspects of thedisclosure.

FIG. 1C is a cross-sectional, schematic view of a glass articlecomprising a glass substrate with an optical film and an ETC coatingdisposed over the substrate, according to some aspects of thedisclosure.

FIG. 2 is a plot of water contact angle vs. reciprocating cycles of aSteel Wool Test on control samples of Corning® Code 5318 glass with anETC coating and comparative samples of Corning® Code 5318 glass withoptical and scratch-resistant films with an ETC coating.

FIG. 3A is a plot of the ratio of OCF₂/OC_(x)F_(y) species in the weartrack of an ETC coating from a Steel Wool Test as measured by x-rayphotoelectron spectroscopy (XPS) vs. reciprocating cycles during theSteel Wool Test on samples of Corning® Code 5318 glass with an ETCcoating and comparative samples of Corning® Code 5318 glass with opticaland scratch-resistant films with an ETC coating.

FIG. 3B is a plot of the atomic percent of total carbon in the weartrack of an ETC coating from a Steel Wool Test as measured by x-rayphotoelectron spectroscopy (XPS) vs. reciprocating cycles during theSteel Wool Test on the same samples as shown in FIG. 3A.

FIG. 4 is a plot of water contact angle vs. reciprocating cycles of aSteel Wool Test on control samples of unpolished Corning® Code 5318glass with an ETC coating and inventive samples of polished Corning®Code 5318 glass (polished to 2 nm and 20 nm of R_(a) surface roughness)with an ETC coating, according to some aspects of the disclosure.

FIG. 5 is a plot of water contact angle vs. reciprocating cycles of aSteel Wool Test on inventive samples of Corning® Code 5318 glass havinga silica film of varying degrees of surface roughness (i.e., from 0.33nm to 1.52 nm of R_(q) surface roughness) with an ETC coating, accordingto some aspects of the disclosure.

FIG. 6 is a plot of water contact angle vs. surface roughness of anouter film surface on inventive samples of Corning® Code 5318 glasshaving a silica film or an AlO_(x)N_(y) film with an ETC coatingdeposited thereon, as measured after 3500 reciprocating cycles of aSteel Wool Test, according to some aspects of the disclosure.

FIG. 7A is a plan view of an exemplary electronic device incorporatingany of the glass articles disclosed herein.

FIG. 7B is a perspective view of the exemplary electronic device of FIG.7A.

DETAILED DESCRIPTION

In the following detailed description, for purposes of explanation andnot limitation, example embodiments disclosing specific details are setforth to provide a thorough understanding of various principles of thepresent disclosure. However, it will be apparent to one having ordinaryskill in the art, having had the benefit of the present disclosure, thatthe present disclosure may be practiced in other embodiments that departfrom the specific details disclosed herein. Moreover, descriptions ofwell-known devices, methods and materials may be omitted so as not toobscure the description of various principles of the present disclosure.Finally, wherever applicable, like reference numerals refer to likeelements.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. As used herein, the term“about” means that amounts, sizes, formulations, parameters, and otherquantities and characteristics are not and need not be exact, but may beapproximate and/or larger or smaller, as desired, reflecting tolerances,conversion factors, rounding off, measurement error and the like, andother factors known to those of skill in the art. When the term “about”is used in describing a value or an end-point of a range, the disclosureshould be understood to include the specific value or end-point referredto. Whether or not a numerical value or end-point of a range in thespecification recites “about,” the numerical value or end-point of arange is intended to include two embodiments: one modified by “about,”and one not modified by “about.” It will be further understood that theendpoints of each of the ranges are significant both in relation to theother endpoint, and independently of the other endpoint.

The terms “substantial,” “substantially,” and variations thereof as usedherein are intended to note that a described feature is equal orapproximately equal to a value or description. For example, a“substantially planar” surface is intended to denote a surface that isplanar or approximately planar. Moreover, “substantially” is intended todenote that two values are equal or approximately equal. In someembodiments, “substantially” may denote values within about 10% of eachother, such as within about 5% of each other, or within about 2% of eachother.

Directional terms as used herein—for example up, down, right, left,front, back, top, bottom—are made only with reference to the figures asdrawn and are not intended to imply absolute orientation.

Unless otherwise expressly stated, it is in no way intended that anymethod set forth herein be construed as requiring that its steps beperformed in a specific order. Accordingly, where a method claim doesnot actually recite an order to be followed by its steps, or it is nototherwise specifically stated in the claims or descriptions that thesteps are to be limited to a specific order, it is in no way intendedthat an order be inferred, in any respect. This holds for any possiblenon-express basis for interpretation, including: matters of logic withrespect to arrangement of steps or operational flow; plain meaningderived from grammatical organization or punctuation; the number or typeof embodiments described in the specification.

As used herein, the singular forms “a,” “an” and “the” include pluralreferents unless the context clearly dictates otherwise. Thus, forexample, reference to a “component” includes aspects having two or moresuch components, unless the context clearly indicates otherwise.

Aspects of the disclosure generally pertain to articles having glass,glass-ceramic and ceramic substrates with lubricious, anti-fingerprintand easy-to-clean (ETC) coatings with high durability and methods ofmaking the same. These lubricious ETC coatings are disposed on one ormore intervening layers (e.g., an optical film, a scratch-resistantfilm, a scratch-resistant film over an optical film, etc.), which aredisposed over the substrate. Further, the optical film and/orscratch-resistant film includes a very low surface roughness (R_(q)),e.g., less than 1.0 nm. In addition, the optical film and/orscratch-resistant film can comprise an average hardness of 12 GPa ormore and/or a total thickness of about 500 nm or more. Without beingbound by theory, reductions in the surface roughness of the film, layeror structure (e.g., the optical film and/or scratch-resistant film)residing beneath the ETC coating tend to significantly increase thedurability of the ETC coating.

Referring to FIG. 1A, an article 100 a is depicted that includes: aglass, glass-ceramic or ceramic substrate 10 comprising a glass,glass-ceramic or ceramic composition. That is, the substrate 10 mayinclude one or more of glass, glass-ceramic, or ceramic materialstherein. The substrate 10 comprises a pair of opposing primary surfaces12, 14. Further, the article 100 a includes an optical film 80 disposedover the primary surface 12, and a scratch-resistant film 90 disposedover the optical film 80. The article 100 a further includes aneasy-to-clean (ETC) coating 70 disposed over the films 80, 90. Inparticular, as shown in FIG. 1A, the ETC coating 70 is located on theouter surface 92 a of the scratch-resistant film 90. Also as shown inFIG. 1A, the optical film 80 has a thickness 84, the scratch-resistantfilm 90 has a thickness 94 and the ETC coating 70 has a thickness 74.

In some embodiments of the article 100 a, the substrate 10 comprises aglass composition. The substrate 10, for example, can comprise aborosilicate glass, an aluminosilicate glass, soda-lime glass,chemically strengthened borosilicate glass, chemically strengthenedaluminosilicate glass, and chemically strengthened soda-lime glass. Thesubstrate may have a selected length and width, or diameter, to defineits surface area. The substrate may have at least one edge between theprimary surfaces 12, 14 of the substrate 10 defined by its length andwidth, or diameter. The substrate 10 may also have a selected thickness.In some embodiments, the substrate has a thickness of from about 0.2 mmto about 1.5 mm, from about 0.2 mm to about 1.3 mm, and from about 0.2mm to about 1.0 mm. In other embodiments, the substrate has a thicknessof from about 0.1 mm to about 1.5 mm, from about 0.1 mm to about 1.3 mm,or from about 0.1 mm to about 1.0 mm.

According to some aspects of the article 100 a, the substrate 10comprises a compressive stress region 50 (see FIG. 1A) that extends fromat least one of the primary surfaces 12, 14 to a selected depth 52. Asused herein, a “selected depth,” (e.g., selected depth 52) “depth oflayer” and “DOC” are used interchangeably to define the depth at whichthe stress in the chemically strengthened alkali aluminosilicate glassarticle described herein changes from compressive to tensile. DOC may bemeasured by a surface stress meter, such as an FSM-6000, or a scatteredlight polariscope (SCALP) depending on the ion exchange treatment. Wherethe stress in the glass article is generated by exchanging potassiumions into the glass article, a surface stress meter is used to measureDOC. Where the stress is generated by exchanging sodium ions into theglass article, SCALP is used to measure DOC. Where the stress in theglass article is generated by exchanging both potassium and sodium ionsinto the glass, the DOC is measured by SCALP, since it is believed theexchange depth of sodium indicates the DOC and the exchange depth ofpotassium ions indicates a change in the magnitude of the compressivestress (but not the change in stress from compressive to tensile); theexchange depth of potassium ions in such glass articles is measured by asurface stress meter. As also used herein, the “maximum compressivestress” is defined as the maximum compressive stress within thecompressive stress region 50 in the substrate 10. In some embodiments,the maximum compressive stress is obtained at or in close proximity tothe one or more primary surfaces 12, 14 defining the compressive stressregion 50. In other embodiments, the maximum compressive stress isobtained between the one or more primary surfaces 12, 14 and theselected depth 52 of the compressive stress region 50.

In some implementations of the article 100 a, as depicted in exemplaryform in FIG. 1A, the substrate 10 is selected from a chemicallystrengthened aluminosilicate glass. In other embodiments, the substrate10 is selected from chemically strengthened aluminosilicate glass havinga compressive stress region 50 extending to a first selected depth 52 ofgreater than 10 μm, with a maximum compressive stress of greater than150 MPa. In further embodiments, the substrate 10 is selected from achemically strengthened aluminosilicate glass having a compressivestress region 50 extending to a first selected depth 52 of greater than25 μm, with a maximum compressive stress of greater than 400 MPa. Thesubstrate 10 of the article 100 a may also include one or morecompressive stress regions 50 that extend from one or more of theprimary surfaces 12, 14 to a selected depth 52 (or depths) having amaximum compressive stress of greater than about 150 MPa, greater than200 MPa, greater than 250 MPa, greater than 300 MPa, greater than 350MPa, greater than 400 MPa, greater than 450 MPa, greater than 500 MPa,greater than 550 MPa, greater than 600 MPa, greater than 650 MPa,greater than 700 MPa, greater than 750 MPa, greater than 800 MPa,greater than 850 MPa, greater than 900 MPa, greater than 950 MPa,greater than 1000 MPa, and all maximum compressive stress levels betweenthese values. In addition, the depth of compression (DOC) or firstselected depth 52 can be set at 10 μm or greater, 15 μm or greater, 20μm or greater, 25 μm or greater, 30 μm or greater, 35 μm or greater andto even higher depths depending on the thickness of the substrate 10 andthe processing conditions associated with generating the compressivestress region 50. Compressive stress (including surface CS) is measuredby a surface stress meter using commercially available instruments suchas the FSM-6000 (i.e., an FSM), as manufactured by Orihara IndustrialCo., Ltd. (Japan). Surface stress measurements rely upon the accuratemeasurement of the stress optical coefficient (SOC), which is related tothe birefringence of the glass. SOC in turn is measured according toProcedure C (Glass Disc Method) described in ASTM standard C770-16,entitled “Standard Test Method for Measurement of Glass Stress-OpticalCoefficient,” the contents of which are incorporated herein by referencein their entirety.

Similarly, with respect to glass-ceramics, the material chosen for thesubstrate 10 of the article 100 a can be any of a wide range ofmaterials having both a glassy phase and a ceramic phase. Illustrativeglass-ceramics include those materials where the glass phase is formedfrom a silicate, borosilicate, aluminosilicate, or boroaluminosilicate,and the ceramic phase is formed from β-spodumene, β-quartz, nepheline,kalsilite, or carnegieite. “Glass-ceramics” include materials producedthrough controlled crystallization of glass. In embodiments,glass-ceramics have about 30% to about 90% crystallinity. Examples ofsuitable glass-ceramics may include Li₂O—Al₂O₃—SiO₂ system (i.e.LAS-System) glass-ceramics, MgO—Al₂O₃—SiO₂ system (i.e. MAS-System)glass-ceramics, ZnO×Al₂O₃×nSiO₂ (i.e. ZAS system), and/or glass-ceramicsthat include a predominant crystal phase including β-quartz solidsolution, β-spodumene, cordierite, and lithium disilicate. Theglass-ceramic substrates may be strengthened using the chemicalstrengthening processes disclosed herein. In one or more embodiments,MAS-System glass-ceramic substrates may be strengthened in Li₂SO₄ moltensalt, whereby an exchange of 2Li⁺ for Mg²⁺ can occur.

With respect to ceramics, the material chosen for the substrate 10 ofthe article 100 a can be any of a wide range of inorganic crystallineoxides, nitrides, carbides, oxynitrides, carbonitrides, and/or the like.Illustrative ceramics include those materials having an alumina,aluminum titanate, mullite, cordierite, zircon, spinel, persovskite,zirconia, ceria, silicon carbide, silicon nitride, silicon aluminumoxynitride or zeolite phase.

As depicted in FIG. 1A, embodiments of the article 100 a can include oneor more of an optical film 80 and a scratch-resistant film 90 disposedover one or more primary surfaces 12, 14 of the substrate 10. As shownin FIG. 1A, one or more of the films 80, 90 are disposed between the ETCcoating 70 and the primary surface 12 of the substrate 10. According tosome implementations, the films 80, 90 can also be disposed over theprimary surface 14 of the substrate 10. With regard to the optical film80, it may include, for example, an anti-reflective (AR) coating,band-pass filter coatings, edge neutral mirror and beam splittercoatings, multi-layer high-reflectance coatings and edge filtercoatings. It should be understood, however, that other functional filmsmay be used to achieve a desired optical property of the resultingarticle 100 a.

Source materials for the optical film 80 may comprise a multi-layercoating, film or structure with each layer having a different refractiveindex. In some embodiments, the multi-layer structure comprises one ormore low refractive index layers and one or more high refractive indexlayers, alternating in their sequencing over one another. For example,the optical film 80 may include a low refractive index material L havinga refractive index from about 1.3 to about 1.6, a medium refractiveindex material M having a refractive index from about 1.6 to about 1.7,or a high refractive index material H having a refractive index fromabout 1.7 to about 3.0. As used herein, the term “index” and “refractiveindex” both refer to the index of refraction of the material. Examplesof suitable low refractive index materials include silica, fused silica,fluorine-doped fused silica, MgF₂, CaF₂, AlF₃, YF₃ and YbF₃. Examples ofsuitable medium refractive index material include Al₂O₃. Examples ofsuitable high refractive index materials include ZrO₂, HfO₂, Ta₂O₅,Nb₂O₅, TiO₂, Y₂O₃, Si₃N₄, SrTiO₃ and WO₃.

In further implementations, suitable high refractive index materials forthe optical film 80 include AlN, AlO_(x)N_(y), SiO_(x)N_(y), andSi_(u)Al_(x)O_(y)N_(z). As understood by those with ordinary skill inthe field of the disclosure with regard to any of the foregoingmaterials (e.g., AlN) for the optical film 80, each of the subscripts,“u,” “x,” “y,” and “z,” can vary from 0 to 1, the sum of the subscriptswill be less than or equal to one, and the balance of the composition isthe first element in the material (e.g., Si or Al). In addition, thosewith ordinary skill in the field can recognize that“Si_(u)Al_(x)O_(y)N_(z)” can be configured such that “u” equals zero andthe material can be described as “AlO_(x)N_(y)”. Still further, theforegoing compositions for the optical film 80 exclude a combination ofsubscripts that would result in a pure elemental form (e.g., puresilicon, pure aluminum metal, oxygen gas, etc.). Finally, those withordinary skill in the art will also recognize that the foregoingcompositions may include other elements not expressly denoted (e.g.,hydrogen), which can result in non-stoichiometric compositions (e.g.,SiN_(x) vs. Si₃N₄). Accordingly, the foregoing materials for the opticalfilm can be indicative of the available space within aSiO₂—Al₂O₃—SiN_(x)—AlN or a SiO₂—Al₂O₃—Si₃N₄—AlN phase diagram,depending on the values of the subscripts in the foregoing compositionrepresentations.

In some embodiments, the source materials for the optical film 80 mayalso include transparent oxide coating (TCO) materials. Examples ofsuitable TCO materials may also include, but are not limited to, indiumtin oxide (ITO), aluminum doped zinc oxide (AZO), zinc stabilized indiumtin oxide (IZO), In₂O₃, and other binary, ternary or quarternary oxidecompounds suitable for forming a doped metal oxide coating.

As used herein, the “AlO_(x)N_(y),” “SiO_(x)N_(y),” and“Si_(u)Al_(x)O_(y)N_(z)” materials in the disclosure include variousaluminum oxynitride, silicon oxynitride and silicon aluminum oxynitridematerials, as understood by those with ordinary skill in the field ofthe disclosure, described according to certain numerical values andranges for the subscripts, “u,” “x,” “y,” and “z”. That is, it is commonto describe solids with “whole number formula” descriptions, such asAl₂O₃. It is also common to describe solids using an equivalent “atomicfraction formula” description such as Al_(0.4)O_(0.6), which isequivalent to Al₂O₃. In the atomic fraction formula, the sum of allatoms in the formula is 0.4+0.6=1, and the atomic fractions of Al and Oin the formula are 0.4 and 0.6 respectively. Atomic fractiondescriptions are described in many general textbooks and atomic fractiondescriptions are often used to describe alloys. (See, e.g.: (i) CharlesKittel, “Introduction to Solid State Physics,” seventh edition, JohnWiley & Sons, Inc., NY, 1996, pp. 611-627; (ii) Smart and Moore, “SolidState Chemistry, An Introduction,” Chapman & Hall University andProfessional Division, London, 1992, pp. 136-151; and (iii) James F.Shackelford, “Introduction to Materials Science for Engineers,” SixthEdition, Pearson Prentice Hall, New Jersey, 2005, pp. 404-418.)

Again referring to the “AlO_(x)N_(y),” “SiO_(x)N_(y),” and“Si_(u)Al_(x)O_(y)N_(z)” materials in the disclosure, the subscriptsallow those with ordinary skill in the art to reference these materialsas a class of materials without specifying particular subscript values.That is, to speak generally about an alloy, such as aluminum oxide,without specifying the particular subscript values, we can speak ofAl_(v)O_(x). The description Al_(v)O_(x) can represent either Al₂O₃ orAl_(0.4)O_(0.6). If v+x were chosen to sum to 1 (i.e. v+x=1), then theformula would be an atomic fraction description. Similarly, morecomplicated mixtures can be described, such as Si_(u)Al_(v)O_(x)N_(y),where again, if the sum u+v+x+y were equal to 1, we would have theatomic fractions description case.

Once again referring to the “AlO_(x)N_(y),” “SiO_(x)N_(y),” and“Si_(u)Al_(x)O_(y)N_(z)” materials in the disclosure, these notationsallow those with ordinary skill in the art to readily make comparisonsto these materials and others. That is, atomic fraction formulas aresometimes easier to use in comparisons. For instance; an example alloyconsisting of (Al₂O₃)O₃(AlN)_(0.7) is closely equivalent to the formuladescriptions Al_(0.448)O_(0.31)N_(0.241) and also Al₃₆₇O₂₅₄N₁₉₈. Anotherexample alloy consisting of (Al₂O₃)_(0.4)(AlN)_(0.6) is closelyequivalent to the formula descriptions Al_(0.438)O_(0.375)N_(0.188) andAl₃₇O₃₂N₁₆. The atomic fraction formulas Al_(0.448)O_(0.31)N_(0.241) andAl_(0.438)O_(0.375)N_(0.188) are relatively easy to compare to oneanother; For instance, we see that Al decreased in atomic fraction by0.01, O increased in atomic fraction by 0.065 and N decreased in atomicfraction by 0.053. It takes more detailed calculation and considerationto compare the whole number formula descriptions Al₃₆₇O₂₅₄N₁₉₈ andAl₃₇O₃₂N₁₆. Therefore, it is sometimes preferable to use atomic fractionformula descriptions of solids. Nonetheless, the use of Al_(v)O_(x)N_(y)is general since it captures any alloy containing Al, O and N atoms.

The source materials of the optical film 80 may be deposited as a singlelayer film or a multilayer film, coating or structure. In someembodiments, a single layer film is formed using a low refractive indexmaterial L as the optical film source material. In other embodiments, asingle layer film is formed using a MgF₂ optical coating sourcematerial. The single layer film may have a selected thickness, i.e.,thickness 84 (see FIG. 1A). In some embodiments, the thickness 84 of asingle layer or multilayer optical film 80 may be greater than or equalto 50 nm, 60 nm, or 70 nm. In some embodiments, the thickness 84 of thesingle layer or multilayer optical film 80 may be less than or equal to2000 nm, 1500 nm, 1000 nm, 500 nm, 250 nm, 150 nm or 100 nm. In furtherembodiments, the thickness 84 of the single layer or multilayer opticalfilm 80 may be 500 nm or more, 1000 nm or more, 1500 nm or more, and allthickness values between these thicknesses. Thickness of the thin filmelements (e.g., scratch-resistant film, layers thereof, etc.) asreported herein was measured by scanning electron microscope (SEM) of across-section, or by optical ellipsometry (e.g., by an n & k analyzer),or by thin film reflectometry. For multiple layer elements (e.g., astack of layers), thickness measurements by SEM are preferred.

The source materials for the optical film 80 may also be deposited as amultilayer coating, film or structure. In some embodiments, themultilayer coating, film or structure of the optical film 80 maycomprise alternating layers of a low refractive index material L, amedium refractive index material M, and a high refractive index materialH. In other embodiments, the multilayer structure may comprisealternating layers of a high refractive index material H and one of (i)a low refractive index material L or (ii) a medium refractive indexmaterial M. The layers may be deposited such that the order of thelayers is H(L or M) or (L or M)H. Each pair of layers, H(L or M) or (Lor M)H, may form a coating period or period. The optical film 80 maycomprise at least one coating period to provide the desired opticalproperties, including, for example and without limitation,anti-reflective properties. In some embodiments, the optical film 80comprises a plurality of coating periods, wherein each coating periodconsisting of one high refractive index material and one of a low ormedium refractive index material. The number of coating periods presentin a multilayer coating may be from 1 to 1000. In some embodiments, thenumber of coating periods present in a multilayer coating may be from 1to 500, from 2 to 500, from 2 to 200, from 2 to 100, or from 2 to 20.

The source materials of the optical film 80 may be selected such thatthe same refractive index materials are used in each coating period insome embodiments, or the optical film source materials may be selectedsuch that different refractive index materials are used in each coatingperiod in other embodiments. For example, in an optical film 80 havingtwo coating periods, the first coating period may comprise SiO₂ aloneand the second period may comprise TiO₂/SiO₂. The ability to vary thealternating layers and coating period may allow a complicated opticalfilter (having the desired optical properties, and including an ARcoating) to be formed.

The thickness of each layer in a coating period of the optical film 80,i.e., the H layer and the L(or M) layer, may independently be from about5 nm to about 200 nm, from about 5 nm to about 150 nm, or from about 25nm to about 100 nm. The multilayer structure may have a thickness 84from about 100 nm to about 2000 nm, from about 150 nm to about 1500 nm,from about 200 nm to about 1250 nm, or from about 400 nm to about 1200nm.

With regard to the scratch-resistant film 90, it may include one or morescratch-resistant layers, films or coatings (e.g., diamond-like carbon,Al₂O₃, AlN, AlO_(x)N_(y), Si₃N₄, SiO_(x)N_(y), Si_(u)Al_(x)O_(y)N_(z),TiN, TiC) as a single-layer structure or a multi-layer structuredisposed over one or more primary surfaces 12, 14 of the substrate 10.As understood by those with ordinary skill in the field of thedisclosure with regard to any of the foregoing materials (e.g., AlN) forthe scratch-resistant film 90, each of the subscripts, “u,” “x,” “y,”and “z,” can vary from 0 to 1, the sum of the subscripts will be lessthan or equal to 1, and the balance of the composition is the firstelement in the material (e.g., Si or Al). In addition, those withordinary skill in the field can recognize that “Si_(u)Al_(x)O_(y)N_(z)”can be configured such that “u” equals zero and the material can bedescribed as “AlO_(x)N_(y)”. Still further, the foregoing compositionsfor the scratch-resistant film 80 exclude a combination of subscriptsthat would result in a pure elemental form (e.g., pure silicon, purealuminum metal, oxygen gas, etc.). Finally, those with ordinary skill inthe art will also recognize that the foregoing compositions may includeother elements not expressly denoted (e.g., hydrogen), which can resultin non-stoichiometric compositions (e.g., SiN_(x) vs. Si₃N₄).Accordingly, the foregoing materials for the optical film can beindicative of the available space within a SiO₂—Al₂O₃—SiN_(x)—AlN or aSiO₂—Al₂O₃—Si₃N₄—AlN phase diagram, depending on the values of thesubscripts in the foregoing composition representations.

In some embodiments, a scratch-resistant film 90 in a multi-layerstructure may further comprise an optical film, such as an AR film, thatis comparable in structure and function to the optical film 80 disposedbeneath it (see FIG. 1A). In a preferred embodiment, thescratch-resistant film 90 comprises an AlO_(x)N_(y) material. In anotherpreferred embodiment, the scratch-resistant film 90 comprises aSi_(u)Al_(x)O_(y)N_(z) material. As shown in FIG. 1A, ascratch-resistant film 90 can be disposed between the ETC coating 70 andthe optical film 80, all of which are disposed over the primary surface12 of the substrate 10. According to some implementations, thescratch-resistant film 90 can also be disposed over the primary surface14 of the substrate 10. The single layer or multilayer scratch-resistantfilm 90 may have a selected thickness, i.e., thickness 94 (see FIG. 1A).In some embodiments, the thickness 94 of a single layer or multilayerscratch-resistant film 90 may be greater than or equal to 50 nm, 60 nm,or 70 nm. In some embodiments, the thickness 94 of the single layer ormultilayer scratch-resistant film 90 may be less than or equal to 3000nm, 2500 nm, 2000 nm, 1500 nm, 1000 nm, 500 nm, 250 nm, 150 nm or 100nm. In further embodiments, the thickness 94 of the single layer ormultilayer scratch-resistant film 90 may be 500 nm or more, 1000 nm ormore, 1500 nm, 2500 nm or more, 3000 nm or more, 3500 nm or more, 4000nm or more, 4500 nm or more, 5000 nm or more, 7500 nm or more, up to10000 nm, and all thickness values between or up to these thicknessvalues. In some embodiments, the scratch-resistant film 90 is thethickest film in the stack of film layers disposed over a surface of thesubstrate.

In preferred embodiments of the article 100 a as shown in FIG. 1A, thetotal of the thickness 84 of the optical film 80, the thickness 94 ofthe scratch-resistant film 90 and any other films below the ETC coating70 is 500 nm or more. In other implementations of the article 100 a, thetotal thickness of the optical and scratch-resistant films 80, 90 (andany other films below the ETC coating 70) is 500 nm or more, 600 nm ormore, 700 nm or more, 800 nm or more, 900 nm or more, 1000 nm or more,1100 nm or more, 1200 nm or more, 1300 nm or more, 1400 nm or more, 1500nm or more, 2000 nm or more, 2500 nm or more, 3000 nm or more, 3500 nmor more, 4000 nm or more, 4500 nm or more, 5000 nm or more, 6000 nm ormore, 7000 nm or more, 8000 nm or more, 9000 nm or more, 10000 nm ormore, and all total thickness values between or up to these thicknessvalues.

Referring now to FIG. 1B, an article 100 b is depicted that includes: aglass, glass-ceramic or ceramic substrate 10 comprising a glass,glass-ceramic or ceramic composition. The article 100 b depicted in FIG.1B is similar to the article 100 a depicted in FIG. 1A, andlike-numbered elements have the same or substantially similar structureand function. The primary difference between article 100 a and article100 b is that the latter does not require an optical film, such as theoptical film 80 depicted in FIG. 1A. With particular regard to thearticle 100 b, its substrate 10 comprises a pair of opposing primarysurfaces 12, 14. Further, the article 100 b includes a scratch-resistantfilm 90 disposed over the primary surface 12. The article 100 b furtherincludes an easy-to-clean (ETC) coating 70 disposed over thescratch-resistant film 90. In particular, as shown in FIG. 1B, the ETCcoating 70 is located on the outer surface 92 b of the scratch-resistantfilm 90. Also as shown in FIG. 1B, the scratch-resistant film 90 has athickness 94, and the ETC coating 70 has a thickness 74.

In preferred embodiments of the article 100 b as shown in FIG. 1B, thetotal of the thickness 94 of the scratch-resistant film 90 and thethickness of any other films (e.g., an optical film comparable instructure and function to the optical film 80 depicted in FIG. 1A)disposed below it and above the primary surface 12 of the substrate 10and/or disposed above it and below the ETC coating 70 is 500 nm or more.In other implementations of the article 100 b, the total thickness ofthe scratch-resistant film 90 and any other layers present below the ETCcoating 70 is 500 nm or more, 600 nm or more, 700 nm or more, 800 nm ormore, 900 nm or more, 1000 nm or more, 1100 nm or more, 1200 nm or more,1300 nm or more, 1400 nm or more, 1500 nm or more, 2000 nm or more, 2500nm or more, 3000 nm or more, 3500 nm or more, 4000 nm or more, 4500 nmor more, 5000 nm or more, and all total thickness values between thesethicknesses.

Referring now to FIG. 1C, an article 100 c is depicted that includes: aglass, glass-ceramic or ceramic substrate 10 comprising a glass,glass-ceramic or ceramic composition. The article 100 c depicted in FIG.1C is similar to the article 100 a depicted in FIG. 1A, andlike-numbered elements have the same or substantially similar structureand function. The primary difference between article 100 a and article100 c is that the latter does not require a scratch-resistant film, suchas the scratch-resistant film 90 depicted in FIG. 1A. With particularregard to the article 100 c, its substrate 10 comprises a pair ofopposing primary surfaces 12, 14. Further, the article 100 c includes anoptical film 80 disposed over the primary surface 12. The article 100 cfurther includes an easy-to-clean (ETC) coating 70 disposed over theoptical film 80. In particular, as shown in FIG. 1C, the ETC coating 70is located on the outer surface 82 c of the optical film 80. Also asshown in FIG. 1C, the optical film 80 has a thickness 84, and the ETCcoating 70 has a thickness 74.

In preferred embodiments of the article 100 c as shown in FIG. 1C, thetotal of the thickness 84 of the optical film 80 and the thickness ofany other films (e.g., a scratch-resistant film comparable in structureto the scratch-resistant film 90 depicted in FIG. 1B) disposed below itand above the primary surface 12 of the substrate 10 and/or disposedabove it and below the ETC coating 70 is 500 nm or more. In otherimplementations of the article 100 c, the total thickness of the opticalfilm 80 and any other layers present below the ETC coating 70 is 500 nmor more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more,1000 nm or more, 1100 nm or more, 1200 nm or more, 1300 nm or more, 1400nm or more, 1500 nm or more, 2000 nm or more, 2500 nm or more, 3000 nmor more, 3500 nm or more, 4000 nm or more, 4500 nm or more, 5000 nm ormore, and all total thickness values between these thicknesses.

The optical film 80 and the scratch-resistant film 90, as present in thearticles 100 a-c, can be deposited using a variety of methods includingphysical vapor deposition (“PVD”), electron beam deposition (“e-beam” or“EB”), ion-assisted deposition-EB (“IAD-EB”), laser ablation, vacuum arcdeposition, thermal evaporation, sputtering, plasma enhanced chemicalvapor deposition (PECVD) and other similar deposition techniques.

Referring again to FIGS. 1A-1C, the outer surface 92 a, 92 b, 82 c ofthe respective scratch-resistant film 90 and optical film 80 employed inthe articles 100 a-c beneath the ETC coating 70 includes a low surfaceroughness, preferably a surface roughness (R_(q)) of less than about 5nm, and more preferably less than about 1.0 nm. In embodiments, thesurface roughness (R_(q)) is held to about 1.0 nm or less, about 0.9 nmor less, about 0.8 nm or less, about 0.7 nm or less, 0.6 nm or less, 0.5nm or less, 0.4 nm or less, 0.3 nm or less, 0.2 nm or less, 0.1 nm orless, and all levels of surface roughness in between these surfaceroughness values. Without being bound by theory, controlling to a lowvalue the surface roughness of the film, layer or structure of theoptical film 80 and/or scratch-resistant film 90 residing beneath theETC coating 70 tends to significantly increase the durability of the ETCcoating 70, as subjected to mechanical interactions. As used herein,“surface roughness (R_(a))” and “surface roughness (Rq)” are given by:

$R_{a} = {{\frac{1}{n}{\sum\limits_{i = 1}^{n}{{y_{i}}\mspace{14mu} {and}\mspace{14mu} R_{q}}}} = \sqrt{\frac{1}{n}{\sum\limits_{i = 1}^{n}y_{i}^{2}}}}$

where y_(i) is the distance of a given measurement, i, from the meanroughness and n is the number of equally spaced points along the outersurface being measured for surface roughness. Further, the surfaceroughness (i.e., R_(a) and R_(q)) of outer surfaces, e.g., surfaces 92a, 92 b and 82 c (see FIGS. 1A-1C) can be measured by atomic forcemicroscopy (AFM) and/or laser interferometry (e.g., with a Zygo® whitelight interferometer) techniques as readily understood by those withordinary skill in the art.

According to some embodiments, the articles 100 a-c depicted in FIGS.1A-1C employ a scratch-resistant film 90 and/or optical film 80 (as thecase may be) with an average hardness of 12 GPa or more. In someaspects, the average hardness of these films can be about 10 GPa ormore, 11 GPa, or more, 12 GPa or more, 13 GPa or more, 14 GPa or more,15 GPa or more, 16 GPa or more, 17 GPa or more, 18 GPa or more, 19 GPaor more, 20 GPa or more, and all average hardness values between thesevalues. As used herein, the “average hardness value” is reported as anaverage of a set of measurements on the outer surface 92 a, 92 b, 82 cof the optical and/or scratch-resistant films 80, 90 using ananoindentation apparatus. More particularly, hardness of thin filmcoatings as reported herein was determined using widely acceptednanoindentation practices. See: Fischer-Cripps, A. C., Critical Reviewof Analysis and Interpretation of Nanoindentation Test Data, Surface &Coatings Technology, 200, 4153-4165 (2006) (hereinafter“Fischer-Cripps”); and Hay, J., Agee, P, and Herbert, E., ContinuousStiffness measurement During Instrumented Indentation Testing,Experimental Techniques, 34 (3) 86-94 (2010) (hereinafter “Hay”). Forcoatings, it is typical to measure hardness and modulus as a function ofindentation depth. So long as the coating is of sufficient thickness, itis then possible to isolate the properties of the coating from theresulting response profiles. It should be recognized that if thecoatings are too thin (for example, less than ˜500 nm), it may not bepossible to completely isolate the coating properties as they can beinfluenced from the proximity of the substrate which may have differentmechanical properties. See Hay. The methods used to report theproperties herein are representative of the coatings themselves. Theprocess is to measure hardness and modulus versus indentation depth outto depths approaching 1000 nm. In the case of hard coatings on a softerglass, the response curves will reveal maximum levels of hardness andmodulus at relatively small indentation depths (less than or equal toabout 200 nm). At deeper indentation depths both hardness and moduluswill gradual diminish as the response is influenced by the softer glasssubstrate. In this case the coating hardness and modulus are taken bethose associated with the regions exhibiting the maximum hardness andmodulus. In the case of soft coatings on a harder glass substrate, thecoating properties will be indicated by lowest hardness and moduluslevels that occur at relatively small indentation depths. At deeperindentation depths, the hardness and modulus will gradually increase dueto the influence of the harder glass. These profiles of hardness andmodulus versus depth can be obtained using either the traditional Oliverand Pharr approach (as described in Fischer-Cripps) or by the moreefficient continuous stiffness approach (see Hay). Extraction ofreliable nanoindentation data requires that well-established protocolsbe followed. Otherwise, these metrics can be subject to significanterrors. The elastic modulus and hardness values reported herein for suchthin films were measured using known diamond nanoindentation methods, asdescribed above, with a Berkovich diamond indenter tip.

The articles 100 a-c described herein may further comprise a cappinglayer of SiO₂ (not shown in FIGS. 1A-1C) on the last layer (of anoptical film 80, scratch-resistant coating 90 or primary surface 12, 14of the substrate 10) in contact with the ETC coating 70. In someaspects, the capping layer can improve the bond between the component ofthe article 100 a-c having the capping layer and the bound ETCcomponent. In some embodiments, the capping layer is added when the lastlayer of the last coating period of the optical film 80 is a highrefractive index layer. In other embodiments, the capping layer is addedwhen the last layer of the last coating period of the optical film 80 isnot SiO₂. In further embodiments, the capping layer may optionally beadded when the last layer of the last coating period of the optical film80 is SiO₂. In some embodiments, the capping layer may have a thicknessfrom about 20 nm to about 400 nm, from about 20 nm to about 300 nm, fromabout 20 nm to about 250 nm, or from about 20 nm to about 200 nm. Inother embodiments, the capping layer may have a thickness from about 1nm to about 400 nm, from about 1 nm to about 300 nm, from about 1 nm toabout 200 nm, from about 1 nm to about 100 nm, from about 1 nm to about50 nm, or from about 1 nm to about 10 nm.

In implementations of the articles 100 a-c, the easy-to-clean (ETC)coating 70 comprises a fluorinated material, e.g., a perfluoropolyether(PFPE) silane, a pefluoroalkylether, a PFPE oil or other suitablefluorinated material. According to some embodiments, the thickness 74 ofthe ETC coating 70 is from about 1 nm to about 20 nm. In other aspects,the thickness 74 of the ETC coating ranges from 1 nm to about 200 nm, 1nm to about 100 nm, and 1 nm to about 50 nm. In some embodiments, theETC coating 70 may have a thickness of from about 0.5 nm to about 50 nm,from about 1 nm to about 25 nm, from about 4 nm to about 25 nm, or fromabout 5 nm to about 20 nm. In other embodiments, the ETC coating mayhave a thickness of from about 10 nm to about 50 nm.

As understood by those with ordinary skill in the field of thedisclosure, various source materials can be used to form the ETC coating70 of the articles 100 a-c depicted in FIGS. 1A-1C. ETC coating sourcematerials may comprise perfluoropolyether (PFPE) silanes,perfluoropolyether (PFPEs) alkoxy silanes, copolymers of these PFPEs andmixtures of these PFPEs. In certain, exemplary embodiments of thearticles of the disclosure, the ETC coating 70 can comprise aperfluoropolyether (PFPE) silane of formula[CF₃CF₂CF₂O)_(a)]_(y)SiX_(4-y) where a is from 5 to 50; y=1 or 2, and Xis —Cl, acetoxy, —OCH₃ or OCH₂H₃, wherein the total perfluoropolyetherchain length is 6-130 carbon atoms from the silicon atom to the end ofthe chain at its greatest length. In other aspects, “a” in the aboveformula can range from about 10 to 30, Further, it should be understoodthat, the above PFPE formula is one of many suitable types of PFPEsuitable for use in the ETC coatings of the disclosure; consequently, itis offered as an exemplary chemistry that is in no way, intended tolimit the formulas or mixtures of formulas suitable for the ETC coatingsof the disclosure. As such, other PFPEs can be employed in the ETCcoatings that vary in the structure of the perfluoropolyether chainand/or attachment chemistry relative to the exemplary form providedabove. For example, an Optool™ UF503 fluorinated coating material fromDaikin Industries is another suitable PFPE that can be employed for theETC coating 70. As used herein, the length of the carbon chain innanometers (“nm”) is the product of the number of carbon-carbon bondsalong the greatest length of the chain multiplied by the carbon-carbonsingle bond length of 0.154 nm. In some embodiments, the carbon chainlength of the perfluoropolyether (PFPE) group can range from about 0.1nm to about 50 nm, from about 0.5 nm to about 2.5 nm, or from about 1 nmto about 20 nm.

As also noted earlier, embodiments of the ETC coating 70 employed in thearticles 100 a-c (see FIGS. 1A-1C) can comprise a PEPE oil, According tosome embodiments, the PFPE oil employed in the ETC coating 70 can besolubilized in an ETC component bound directly to the optical film 80and/or scratch-resistant film 90. In general, PIPE oils arecharacterized by oxidation resistance. In other aspects, the PFPE oil ofthe ETC coating 70 is a discreet layer disposed over an ETC componentbound directly to the optical film 80 and/or scratch-resistant film 90.In further aspects, the PFPE oil of the ETC coating 70 is a combinationof solubilized and discreet layers. According to some embodiments, thePEPE oil employed in the ETC coating 70 can comprise a Solvay Fomblin® Ztype oil, a Fomblin® Y type oil, a Fomblin® K type oil, Krytox™ K typeoil from The Chemours Company, a Demnum™ type oil from Daikin Industriesor other similar PRE oil.

In embodiments, articles 100 a-c of the disclosure (see FIGS. 1A-1C)include an ETC coating 70 that is characterized by a high durability.Accordingly, some embodiments of the articles 100 a-c an exposed surfaceof the ETC coating 70 comprises an average contact angle with water of70 or more degrees after being subjected to 2000 reciprocating cyclesunder a load of 1 kg, according to a Steel Wool Test (i.e., as describedbelow). The exposed surface of the ETC coating 70 can also comprise anaverage contact angle with water of 70 or more degrees after beingsubjected to 3500 reciprocating cycles under a load of 1 kg according tothe Steel Wool Test. In other aspects, an average contact angle of 70 ormore degrees, 75 degrees, 80 degrees, 85 degrees, 90 degrees, 95degrees, 100 degrees, 105 degrees, 110 degrees, or 115 degrees(including all average contact angles between these levels) with wateris retained by the exposed surface of the ETC coating 70 after 2000, or3500, of such cycles according to the Steel Wool Test.

As used herein, the “Steel Wool Test” is a test employed to determinethe durability of an ETC coating 70 disposed over a glass, glass-ceramicor ceramic substrate (e.g., substrate 10 as shown in FIGS. 1A-1C)employed in the articles of the disclosure (e.g., articles 100 a-cdepicted in FIGS. 1A-1C). At the beginning of a Steel Wool Test, a watercontact angle is measured on the particular sample one or more times toobtain a reliable initial water contact angle. These water contact anglemeasurements can be conducted using a Kruss GmbH DSA100 drop shapeanalyzer or similar instrument. After the initial water contact angle ismeasured, a pad of Bonstar #0000 steel wool is affixed to an arm of aTaber® Industries 5750 linear abraser instrument. The steel wool pad wasthen allowed to make contact with the sample (on the ETC coating) undera load of 1 kg and set to reciprocate at 60 cycles/min. The averagecontact angle is then measured on the sample after 2000 cycles, 3500cycles and/or another specified duration.

In embodiments, the articles 100 a-c (see FIGS. 1A-1C) can comprise ahaze through the ETC coating 70 and the glass, glass-ceramic or ceramicsubstrate 10 of less than or equal to about 5 percent. In certainaspects, the haze is equal to or less than 5 percent, 4.5 percent, 4percent, 3.5 percent, 3 percent, 2.5 percent, 2 percent, 1.5 percent, 1percent, 0.75 percent, 0.5 percent, or 0.25 percent (including alllevels of haze between these levels) through the ETC coating 70 and theglass substrate 10. In other embodiments, the articles 100 a-c comprisean optical film 80 and/or scratch-resistant film 90 that is by naturehazy; consequently, the level of haze through the ETC coating 70, theoptical film 80 and/or scratch-resistant film 90, and the substrate 10can be set at 10 percent or higher, 5 percent or higher, or another hazelevel above these lower haze limits. In other implementations, articles100 a-c that incorporate appreciable haze (>5%) as part of theirfunction, and also comprise an ETC coating with high durability, e.g.,as comprising an average contact angle with water of 100 degrees or moreafter being subjected to 2000 reciprocating cycles, or 3500reciprocating cycles, under a load of 1 kg according to the Steel WoolTest. As used herein, the “haze” attributes and measurements reported inthe disclosure are as measured on, or otherwise based on measurementsfrom, a BYK-Gardner haze meter using an aperture over the source porthaving a dimeter of 7 mm.

The ETC coating 70 employed in the articles 100 a-c of the disclosurecan be applied in various ways over the outer surfaces 92 a, 92 b and 82c of the scratch-resistant films 90 and optical films 80 (see FIGS.1A-1C). According to some embodiments, the ETC coating 70 can bedeposited by various methods, including but not limited to, spraycoating, dip coating, spin coating, and vapor deposition. Vapordeposition approaches for depositing the ETC coating 70 can include, butare not limited to, physical vapor deposition (“PVD”), electron beamdeposition (“e-beam” or “EB”), ion-assisted deposition-EB (“IAD-EB”),laser ablation, vacuum arc deposition, thermal evaporation, sputtering,plasma enhanced chemical vapor deposition (PECVD) and other similarvapor deposition techniques.

EXAMPLES

The following examples represent certain non-limiting embodiments of thedisclosure.

Example 1

Glass article samples were prepared that include Corning® Code 2320glass substrates. These samples had a thickness of 1 mm and wereion-exchanged to develop a compressive stress region with a DOC of 47.1μm and a maximum compressive stress of 883.7 MPa. Further, a SiO₂capping layer was deposited on these glass substrates by PVD immediatelyprior to application of an ETC coating. The ETC coating (i.e., a CekoCo., Ltd. ETC coating with Fomblin-type PFPE structure) was also appliedby PVD under a combination of temperature and time conditions suitableas understood by those with ordinary skill for this particular Ceko ETCcoating. These samples were deemed as a control and labeled “Glass” (seeFIG. 2). A separate group of samples was prepared with three sputteredAlO_(x)N_(y)/SiO₂-based optical and scratch-resistant film structures,P86, P92, and P95, having a total thickness of about 2192 nm, 2283 nm,and 2429 nm, respectively, with an outermost SiO₂ capping layer (i.e.,having thicknesses of 14 nm, 65 nm and 82.2 nm for the P86, P92 and P95structures, respectively), followed by an ETC coating as employed in the“Glass” samples. These samples are deemed as comparative samples withregard to the articles of the disclosure and labeled “Comp. Ex. 2A”,“Comp. Ex. 2B” and “Comp. Ex. 2C” in FIG. 2.

Referring now to FIG. 2, a plot of water contact angle vs. reciprocatingcycles of a Steel Wool Test conducted on the “Glass” and “Comp. Ex. 2A,2B and 2C” samples is provided. FIG. 2 shows that the durability of theETC coating is significantly reduced in the samples having theAlO_(x)N_(y)/SiO₂-based optical and scratch-resistant film structures ascompared to the ETC coating on the “Glass” samples without the opticaland scratch-resistant films. At zero cycles, the “Glass” and “Comp. Ex.2A, 2B and 2C” samples were measured with a contact angle from about115.0 to 117.1 degrees. During the Steel Wool Test, however, the watercontact angle falls below 100 degrees for the “Comp. Ex. 2A, 2B and 2C”samples after 2000 cycles (e.g., from 82.4 to 91.7 degrees) andcontinues to fall, as measured after 3500 cycles (e.g., from 62.3 to79.0 degrees). In comparison the control “Glass” samples remained at113.7 and 112.6 degrees at 2000 and 3500 cycles, respectively, duringthe Steel Wool Test.

Further, atomic force microscopy (AFM) measurements were made on the“Glass” control samples and the “Comp. Ex. 2A,” “Comp. Ex. 2B” and“Comp. Ex. 2C” samples to determine surface roughness and the thicknessof the top-most SiO₂ layer in these structures that resides beneath theETC coating. Table 1 below shows the results of these measurements forall of the samples except the “Comp. Ex. 2A” samples. In view of theresults in Table 1 and the plot shown in FIG. 2 (which does include datafrom the “Comp. Ex. 2A” samples), it is believed that the surfaceroughness of the top-most SiO₂ layer of the “Glass” control samples andthe optical/scratch-resistant film structure of the “Comp. Ex. 2A,”“Comp. Ex. 2B” and “Comp. Ex. 2C” samples influences ETC coatingdurability, as quantified by the Steel Wool Test.

TABLE 1 Surface SiO₂ Contact Contact Angle Contact Angle roughness,thickness Angle after after 2000 after 3500 R_(q) (nm) (nm) 0 cycles (°)cycles (°) cycles (°) Glass 0.22 14 117.1 113.7 112.6 Comp. Ex. 2B 2.8683 115.6 91.7 73.4 Comp. Ex. 2C 3.09 19 115.0 82.4 62.3

Example 2

FIG. 3A is a plot of the ratio of OCF₂/OC_(x)F_(y) species in the weartrack of an ETC coating, as measured by x-ray photoelectron spectroscopy(XPS). In particular, the XPS measurements shown in FIG. 3A are plottedvs. reciprocating cycles during the Steel Wool Test on control samplesof Corning® Code 5318 glass with an ETC coating (i.e., the “Glass”samples from Example 1) and on comparative samples of Corning® Code 5318glass with optical and scratch-resistant films with an ETC coating(i.e., the “Comp. Ex. 2B” and “Comp. Ex. 2C”). As shown in the datapresented in FIG. 3A associated with the comparative samples withoptical and scratch-film structures, the decrease in theOCF₂/OC_(x)F_(y) ratio as a function of cycles during the Steel Wooltest is indicative of the degradation of the Fomblin-type structure inthe ETC coating during the mechanical abrasion of the Steel Wool Test.By 2000 cycles on test, the OCF₂/OC_(x)F_(y) ratio is about ⅙^(th) ofits initial value at 0 cycles. It is also noteworthy that theOCF₂/OC_(x)F_(y) ratio does not degrade as a function of Steel Wool Testcycles for the control sample.

FIG. 3B is a plot of the atomic percent of total carbon in the weartrack of an ETC coating, as measured by x-ray photoelectron spectroscopy(XPS). In particular, the XPS measurements shown in FIG. 3B are plottedvs. reciprocating cycles during the Steel Wool Test on control samplesof Corning® Code 5318 glass with an ETC coating (i.e., the “Glass”samples from Example 1) and on comparative samples of Corning® Code 5318glass with optical and scratch-resistant films with an ETC coating(i.e., the “Comp. Ex. 2B” and “Comp. Ex. 2C”). As shown in the datapresented in FIG. 3B associated with the comparative samples withoptical and scratch-film structures, the hydrocarbon fraction isincreased in the comparative samples as the Fomblin-type structure inthe ETC coating is degraded during the mechanical abrasion of the SteelWool Test. It is also noteworthy that the amount of hydrocarbons isessentially unchanged as a function of Steel Wool Test cycles for thecontrol sample.

Taken together, and without being bound by theory, it is believed thatthe data in FIGS. 3A and 3B suggest that the mechanism of degradation ofthe ETC coating during the Steel Wool Test is not removal of the bondedETC portion at the silane head group, but rather polymer chain breakagealong the pefluoroalkylether structure. As such, it is also believedthat the increased roughness associated with the underlying optical andscratch-resistant films of the comparative samples (i.e., as relative tothe control sample without such films) leads to increased ETCdegradation during the Steel Wool Test.

Example 3

Glass article samples were prepared that include Corning® Code 5318glass substrates. These samples had a thickness of 0.5 mm and wereion-exchanged to develop a compressive stress region with a DOC of 81 μmand a maximum compressive stress of 840 MPa. Two groups of these sampleswere polished to a surface roughness (R_(a)) of 2 nm and 20 nm,respectively, and one group was left in an unpolished state with asurface roughness (R_(a)) of 0.2 nm. Further, a 10 nm SiO₂ capping layerwas deposited on all of these glass substrates by a PVD process. An ETCcoating (i.e., a Daikin UF505 ETC coating) was then applied by a sprayprocess and cured on all of these samples for 120° C. for 30 minutesfollowed by a 10 minute rinse in 3M™ Novec™ 7200 Engineered Fluid withsonication.

FIG. 4 is a plot of water contact angle vs. reciprocating cycles of aSteel Wool Test, as conducted on the samples prepared according to thisExample. FIG. 4 shows that the surface roughness of the outer surfacebeneath the ETC coating plays a substantial role in the durability ofthe ETC coating. In particular, the samples having an outer surface witha surface roughness (R_(a)) of 0.2 nm remained with a water contactangle of about 100 degrees after 2000 cycles, and after 3500 cycles, ofthe Steel Wool Test. In contrast, the samples having an outer surfacewith a surface roughness (R_(a)) of 2 nm and 20 nm degraded during theSteel Wool Test, such that a water contact angle of less than 100degrees was observed after 2000 cycles, and after 3500 cycles, duringthe Steel Wool Test.

Example 4

Glass article samples were prepared that include Corning® Code 5318glass substrates. These samples had a thickness of 1.0 mm and wereion-exchanged to develop a compressive stress region with a DOC of 70.5μm and a maximum compressive stress of 812.7 MPa. Further, a SiO₂capping layer was deposited on these glass substrates with aPlasma-Therm Versaline system using a high density plasma chemical vapordeposition (HDPCVD) process. In particular, SiO₂ layers were depositedwith varying thicknesses and surface roughness levels (e.g., from 18.5to 368.9 nm in thickness and from 0.329 nm to 1.52 nm in surfaceroughness, R_(q)) with the HDPCVD process, with no post-depositionpolishing steps, to develop six groups of samples. The surface roughnessand thickness data associated with these samples is listed below inTable 2, both of which were measured using AFM techniques as understoodby those with ordinary skill in the field of this disclosure. Finally,an ETC coating (i.e., a Daikin UF503 ETC coating) was then applied by aspray process and cured on all of these samples for 120° C. for 30minutes followed by a 10 minute rinse in 3M™ Novec™ 7200 EngineeredFluid with sonication.

FIG. 5 is a plot of water contact angle vs. reciprocating cycles of aSteel Wool Test, as conducted on the samples prepared according to thisExample. The same data is also reported in tabular form in Table 2below. FIG. 5 shows that the surface roughness of the outer SiO₂ surfacebeneath the ETC coating plays a substantial role in the durability ofthe ETC coating. As is evident from Table 2 and FIG. 5, the contactangle degrades below 100 degrees after 2000 cycles during the Steel WoolTest for samples having a surface roughness, R_(q), of greater than 0.7nm. Moreover, the degradation in contact angle below 100 degrees isobserved after about 1000 cycles during the Steel Wool Test for thesamples having a surface roughness, R_(q), of greater than 0.7 nm. Inaddition, as is evident from FIG. 5, the samples having a surfaceroughness, R_(q), of about 1 nm are observed with a contact angle ofabout 110 degrees after 50 cycles during the Steel Wool Test and above95 degrees after 500 cycles during the Steel Wool Test.

TABLE 2 Thickness R_(q) No Steel Wool 50 SW 100 SW 200 SW 500 SW 1000 SW2000 SW (nm) (nm) (SW) cycles cycles cycles cycles cycles cycles cycles18.5 0.329 116.3 115.9 114.0 113.7 113.0 112.2 105.5 33.7 0.43 116.6116.0 115.1 113.2 112.8 112.3 111.9 64.4 0.657 115.6 114.9 113.8 113.8113.1 110.7 109.3 95.2 0.707 115.1 113.1 112.4 110.9 109.0 87.3 82.3155.8 1.02 100.4 110.6 106.0 105.2 97.6 80.3 75.5 368.9 1.52 115.4 108.8150.8 96.5 94.9 85.0 80.1

Example 5

FIG. 6 is a plot of water contact angle vs. surface roughness of anouter surface of inventive samples of Corning® Code 5318 glass having asilica film or a silica film and an AlO_(x)N_(y) optical and/orscratch-film structure, all with an ETC coating deposited thereon (i.e.,a Ceko Co., Ltd. ETC coating applied with a physical vapor depositiontechnique). Those samples comprising a glass substrate, silica film andan ETC coating are characterized by a surface roughness (R_(a)) of 0.3nm (i.e., as shown in FIG. 6 with a solid diamond symbol). The remainingsamples comprising a glass substrate, silica film, AlO_(x)N_(y) opticaland/or scratch-film structure and an ETC coating are characterized by asurface roughness (R_(a)) of about 0.6 nm to about 1.8 nm (i.e., asshown in FIG. 6 with an open diamond symbol). The contact angle resultsin FIG. 6 were obtained after subjecting the samples to 3500 cyclesduring the Steel Wool Test. Further, the samples with the AlO_(x)N_(y)optical and/or scratch resistant-film structure were obtained bysputtering the AlON-type material directly onto 5318 glass substrates.As is evident from the data shown in FIG. 6, the contact anglecorrelates with the surface roughness of the outer surface of the filmbeneath the ETC coating (i.e., the outer surface of the silica film ofthe samples denoted by an open diamond symbol and the outer surface ofthe AlO_(x)N_(y) optical and/or scratch-film structure of the samplesdenoted by a solid diamond symbol). In particular, those samples with asurface roughness, R_(a), of greater than 1 nm exhibited a contact ofangle of less than 100 degrees after the 3500 cycles during the SteelWool Test. In contrast, those samples with a surface roughness, R_(a),of less than 1 nm exhibited a contact angle of 100 degrees or greaterafter the 3500 cycles during the Steel Wool Test. Further, those skilledin the field of the disclosure will recognize that R_(a) and R_(q), thearithmetic average of absolute values and root mean squared (RMS)surface roughness, respectively, are strongly correlated, with R_(q)often slightly higher than R_(a) for the same surface. Accordingly,those with ordinary skill in the art can scale the Ra values shown inFIG. 6 to reflect R_(q) values, all of which will be slightly larger anddemonstrate the same trend observed in the R_(a) values currentlyreported in FIG. 6.

The articles disclosed herein may be incorporated into a device articlesuch as a device article with a display (or display device articles)(e.g., consumer electronics, including mobile phones, tablets,computers, navigation systems, wearable devices (e.g., watches) and thelike), architectural device articles, transportation device articles(e.g., automotive, trains, aircraft, sea craft, etc.), appliance devicearticles, or any device article that benefits from some transparency,scratch-resistance, abrasion resistance or a combination thereof. Anexemplary device article incorporating any of the articles disclosedherein is shown in FIGS. 7A and 7B. Specifically, FIGS. 7A and 7B show aconsumer electronic device 7100 including a housing 7102 having front7104, back 7106, and side surfaces 7108; electrical components (notshown) that are at least partially inside or entirely within the housingand including at least a controller, a memory, and a display 7110 at oradjacent to the front surface of the housing; and a cover substrate 7112at or over the front surface of the housing such that it is over thedisplay. In some embodiments, the cover substrate 7112 may include anyof the articles disclosed herein. In some embodiments, at least one of aportion of the housing or the cover glass comprises the articlesdisclosed herein.

Many variations and modifications may be made to the above-describedembodiments of the disclosure without departing substantially from thespirit and various principles of the disclosure. All such modificationsand variations are intended to be included herein within the scope ofthis disclosure and protected by the following claims.

What is claimed is:
 1. An article, comprising: a glass, glass-ceramic orceramic substrate comprising a primary surface; at least one of anoptical film and a scratch-resistant film disposed over the primarysurface; and an easy-to-clean (ETC) coating comprising a fluorinatedmaterial that is disposed over an outer surface of the at least one ofan optical film and a scratch-resistant film, wherein the at least oneof an optical film and a scratch-resistant film comprises an averagehardness of 10 GPa or more, and wherein the outer surface of the atleast one of an optical film and a scratch-resistant film comprises asurface roughness (R_(q)) of less than 1.0 nm.
 2. The article accordingto claim 1, wherein the outer surface of the at least one of an opticalfilm and a scratch-resistant film comprises a surface roughness (R_(q))of less than 0.7 nm.
 3. The article according to claim 1, wherein theouter surface of the at least one of an optical film and ascratch-resistant film comprises a surface roughness (R_(q)) of lessthan 0.5 nm.
 4. The article according to claim 1, wherein an exposedsurface of the ETC coating comprises an average contact angle with waterof 100 degrees or more after being subjected to 2000 reciprocatingcycles under a load of 1 kg according to a Steel Wool Test.
 5. Thearticle according to claim 1, wherein an exposed surface of the ETCcoating comprises an average contact angle with water of 100 degrees ormore after being subjected to 3500 reciprocating cycles under a load of1 kg according to a Steel Wool Test.
 6. The article according to claim1, wherein the ETC coating comprises a perfluoropolyether (PFPE) silane.7. The article according to claim 1, wherein the at least one of anoptical film and a scratch-resistant film comprises a scratch-resistantfilm comprising an AlO_(x)N_(y) material, a Si_(u)Al_(x)O_(y)N_(z)material, or a SiO_(x)N_(y) material.
 8. The article according to claim1, wherein the at least one of an optical film and a scratch-resistantfilm is an optical film and a scratch-resistant film, thescratch-resistant film disposed over the optical film, wherein the outersurface of the at least one of an optical film and a scratch-resistantfilm comprises a surface roughness (R_(q)) of from about 0.1 nm to lessthan 1 nm, wherein the optical film comprises a plurality of alternatinghigh index and low index layers with a first low index layer on theprimary surface of the substrate, and further wherein each low indexlayer comprises SiO₂, fused SiO₂, fluorine-doped fused SiO₂, MgF₂, CaF₂,AlF₃, YF₃ or YbF₃ and each high index layer comprises AlN, AlO_(x)N_(y),SiO_(x)N_(y) or Si_(u)Al_(x)O_(y)N_(z).
 9. The article according toclaim 1, wherein the at least one of an optical film and ascratch-resistant film is an optical film and a scratch-resistant film,wherein the optical film has a thickness less than or equal to 500 nmand the scratch-resistant film has a thickness less than or equal to 150nm.
 10. The article according to claim 1, wherein the at least one of anoptical film and a scratch-resistant film is an optical film and ascratch-resistant film, wherein the optical film has a thickness lessthan or equal to 250 nm and the scratch-resistant film has a thicknessless than or equal to 150 nm.
 11. An article, comprising: a glass,glass-ceramic or ceramic substrate comprising a primary surface; atleast one of an optical film and a scratch-resistant film disposed overthe primary surface; and an easy-to-clean (ETC) coating comprising afluorinated material that is disposed over an outer surface of the atleast one of an optical film and a scratch-resistant film, and furtherwherein the outer surface of the at least one of an optical film and ascratch-resistant film comprises a surface roughness (R_(q)) of lessthan 1.0 nm.
 12. The article according to claim 11, wherein the outersurface of the at least one of an optical film and a scratch-resistantfilm comprises a surface roughness (R_(q)) of less than 0.7 nm.
 13. Thearticle according to claim 11, wherein the outer surface of the at leastone of an optical film and a scratch-resistant film comprises a surfaceroughness (R_(q)) of less than 0.5 nm.
 14. The article according toclaim 11, wherein an exposed surface of the ETC coating comprises anaverage contact angle with water of 100 degrees or more after beingsubjected to 2000 reciprocating cycles under a load of 1 kg according toa Steel Wool Test.
 15. The article according to claim 11, wherein anexposed surface of the ETC coating comprises an average contact anglewith water of 100 degrees or more after being subjected to 3500reciprocating cycles under a load of 1 kg according to a Steel WoolTest.
 16. The article according to claim 11, wherein the ETC coatingcomprises a perfluoropolyether (PFPE) silane.
 17. The article accordingto claim 11, wherein the at least one of an optical film and ascratch-resistant film comprises a scratch-resistant film comprising anAlO_(x)N_(y) material, a Si_(u)Al_(x)O_(y)N_(z) material, or aSiO_(x)N_(y) material.
 18. The article according to claim 11, whereinthe at least one of an optical film and a scratch-resistant film is anoptical film and a scratch-resistant film, wherein the optical film hasa thickness less than or equal to 500 nm and the scratch-resistant filmhas a thickness less than or equal to 150 nm.
 19. The article accordingto claim 11, wherein the at least one of an optical film and ascratch-resistant film is an optical film and a scratch-resistant film,wherein the optical film has a thickness less than or equal to 250 nmand the scratch-resistant film has a thickness less than or equal to 150nm.
 20. A consumer electronic product, comprising: a housing having afront surface, a back surface and side surfaces; electrical componentsprovided at least partially within the housing, the electricalcomponents including at least a controller, a memory, and a display, thedisplay being provided at or adjacent the front surface of the housing;and a cover glass disposed over the display, wherein at least one of aportion of the housing or the cover glass comprises the article of claim1.